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form a cage ± like structure around smaller guest molecules. The most common guest molecules are methane, ethane, propane, isobutene, normal butane, nitrogen, carbon dioxide, and hydrogen sulphide, of which methane occurs most abundantly in natural hydrates. Several different hydrate structures are known. The structure of hydrate is governed by the size of guest molecule, temperature, and pressure. Where the structure may change from structure II hydrate at low temperatures and pressure to structure I at high temperatures and pressure. The two most common structures are STRUCTURE I and STRUCTURE II. Type I forms with smaller molecules such as methane, ethane, hydrogen sulphide, and carbon dioxide, whereas structure II is a diamond lattice, formed by large molecules such as propane, and isobutene. Furthermore, The existence of a new hydrate structure, type H. Some iso-paraffins and cyclo-alkanes larger than pentane are known to form structure H hydrates. However, little is known about type H structures. The conditions that influence hydrate formation are; the gas being (1) at the appropriate temperature and pressure. and (2) at or below its water dew point. Other factors that affect, but are not necessary for formation include; turbulence, nucleation sites, surface for agglomeration, and salinity of the system. For any particular composition of gas at a given pressure, there is a temperature below which hydrates will form and above which hydrate will not form and as a general rule, when the pressure of the gas stream increases or as the gas becomes colder, the tendency to form hydrates increases. Gas hydrates may be of potential benefit both as a important source of hydrocarbon energy and as a means of storing and transmitting natural gas, they represent a severe operational problem, as hydrate crystals may deposit on the pipe wall and accumulate as large plugs that can completely shut in production and damaging production facilities. The remediation of hydrate blockages can present significant technical difficulties with major cost implications.
Hydrate Locus for Natural Gas Components The thermodynamic stability of hydrates, with respect to temperature and pressure, may be presented by the hydrate curve and the thermodynamic understanding of hydrates indicate the conditions of temperature, pressure and compositions that hydrate will form and more importantly whether they will cause blockage.. The hydrate curve represents the thermodynamic boundary between hydrate stability and dissociation.
Prediction of Hydrate Formation Conditions There are three popular methods: 1.) K ± Factor method: hydrate temperature can be predicted using vapour ± solid(hydrate) equilibrium constant and the basic equation for this prediction developed by Carson and Katz in 1942, is
where yi = mole fraction of component i in gas on a water-free basis, Ki = vapor±solid equilibrium constant for component i, n = number of components.
. Below are two charts for the K constant for the carson and katz and the mann et al at different temperatures and pressures.Ki = where xi is mole fraction of component i in solid on a water-free basis.) Nitrogen is a non-hydrate former and if n-butane is present in mole fractions less than 5% has the same Ki as ethane. Limitations Result for sweet gases is reasonable but in-appropriate for pressures greater than 1000psia. Mann et al presented new K-value charts that cover a wide range of temperature and pressure and can be alternate for carson and katz which are not functions of structure or composition. Assumptions 1. In liu of this limitation.
it becomes colder. TYPE OF INHIBITORS .e such pipelines could experience hydrate at some point. The last two methods are used for offshore transmission line. butane. The simplest is an external hot-water jacket for a pipe-in-pipe system. Hydrate Prevention Techniques As gas flow through pipelines.Thermal method: This method employs the conservation or introduction of heat to maintain the flowing mixture outside the hydrate formation range. METHODS . Therefore using this chart for other compositions other than this will produce an erroneous result. ethylene glycol. calcium chloride. . . and normal pentane. propane.Increasing the salt content of the thermodynamic inhibitors by injecting electrolyte solutions such as sodium chloride. and potassium chloride. while introduction of heat may be achieved by conductive or inductive heat tracing. regenerated.Thermodynamic Inhibitors. but is fairly accurate if the CO2 is less than about 5% mol%. And uses the Katz gravity chart which can be used to predict the approximate pressures and temperatures for hydrate formation provided hydrate exist in the pressure-temperature region above the appropriate gravity curve. They cause the hydrate stability point to be displaced to a lower temperature and/or pressure. i.Keeping the fluid warmer than the hydrate formation temperature or operate at a pressure less than the hydrate formation pressure (usually for onshore gas transmission line).2) Baillie and Wichert Method : This method is a chat method in pressure range of 100 to 4000psia for natural gas containing up to 50% hydrogen sulphide and up to 10% propane and may not apply for sweet gas mixture containing CO2.Chemical Inhibition: It¶s an alternative to the thermal method in which chemical inhibitors are injected at the wellhead to prevent hydrate formation by depressing the hydrate temperature below that of the pipeline operating temperature. which are: methanol. Tri ethylene glycol at high enough concentration. . and re-injected. . The curves derived in this chart are achieved using methane. The principal factor in selecting inhibitors is whether the spent chemical will be recovered. ethane. Control of hydrates relies on keeping the system condition out of the regions in which hydrates are stable. 3) Gas Gravity Method: This method employs gas analysis. Conservation of heat may be achieved by insulation.
Accurate prediction of this low concentration of inhibitor concentration is required for cost effective design and operation of multi-phase pipelines. . namely: Kinetic Hydrate Inhibitors. Therefore inhibitors must be present in low concentrations to avoid hydrate formation. and Anti-agglomerates and are present in low concentrations.- Low Dosage hydrate Inhibitors: Operate on the basis of not changing the thermodynamic conditions of the system. They are of two types. instead they modify the rheological properties of the system.